High-pressure behavior and crystal-fluid interaction under extreme conditions in paulingite [PAU-topology]

G. Diego Gatta, Katharina S. Scheidl, Thomas Pippinger, Roman Skála, Yongjae Lee, Ronald Miletich

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The compressional behavior and the P-induced crystal-fluid interaction of a natural paulingite-K have been explored on the basis of in-situ single-crystal and powder X-ray diffraction, and in-situ single-crystal Raman spectroscopy with a diamond anvil cell and a series of diverse pressure-transmitting fluids (i.e., silicone-oil, methanol:ethanol = 4:1, methanol:ethanol:water = 16:3:1). No evidence of any phase transition was observed within the P-range investigated, independent on the used P-fluids. The compressional behavior of paulingite is significantly different in response to the different nature of the P-fluids. A drastically lower compressibility is observed when the zeolite is compressed in methanol:ethanol or, even more noticeably, in methanol:ethanol:water mix. We ascribe this phenomenon to the different crystal-fluid interaction at high pressure: (1) silicone-oil is a "non-penetrating" P-medium, because of its polymeric nature, whereas (2) methanol-ethanol and water are "penetrating" P-fluids. The P-induced penetration processes appear to be completely reversible on the basis of the X-ray diffraction data alone. The Raman spectra collected after the high-pressure experiments show, unambiguously, that a residual fraction of methanol (and/or ethanol and probably even extra H2O) still resides in the zeolitic sub-nanocavities; such molecules are spontaneously released after a few days at atmospheric pressure. The actual compressibility of paulingite-K is that obtained by the compression experiment in silicone-oil, with an isothermal bulk modulus K0 = β0-1 = 18.0(1.1) GPa. Paulingite appears to be one of the softest zeolite ever found.

Original languageEnglish
Pages (from-to)34-41
Number of pages8
JournalMicroporous and Mesoporous Materials
Volume206
Issue numberC
DOIs
Publication statusPublished - 2015 Apr 1

Fingerprint

Methanol
Ethanol
ethyl alcohol
topology
methyl alcohol
Topology
Silicone Oils
Crystals
Fluids
fluids
silicones
Silicones
crystals
Zeolites
oils
interactions
Compressibility
compressibility
Water
Single crystals

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials

Cite this

Gatta, G. Diego ; Scheidl, Katharina S. ; Pippinger, Thomas ; Skála, Roman ; Lee, Yongjae ; Miletich, Ronald. / High-pressure behavior and crystal-fluid interaction under extreme conditions in paulingite [PAU-topology]. In: Microporous and Mesoporous Materials. 2015 ; Vol. 206, No. C. pp. 34-41.
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abstract = "The compressional behavior and the P-induced crystal-fluid interaction of a natural paulingite-K have been explored on the basis of in-situ single-crystal and powder X-ray diffraction, and in-situ single-crystal Raman spectroscopy with a diamond anvil cell and a series of diverse pressure-transmitting fluids (i.e., silicone-oil, methanol:ethanol = 4:1, methanol:ethanol:water = 16:3:1). No evidence of any phase transition was observed within the P-range investigated, independent on the used P-fluids. The compressional behavior of paulingite is significantly different in response to the different nature of the P-fluids. A drastically lower compressibility is observed when the zeolite is compressed in methanol:ethanol or, even more noticeably, in methanol:ethanol:water mix. We ascribe this phenomenon to the different crystal-fluid interaction at high pressure: (1) silicone-oil is a {"}non-penetrating{"} P-medium, because of its polymeric nature, whereas (2) methanol-ethanol and water are {"}penetrating{"} P-fluids. The P-induced penetration processes appear to be completely reversible on the basis of the X-ray diffraction data alone. The Raman spectra collected after the high-pressure experiments show, unambiguously, that a residual fraction of methanol (and/or ethanol and probably even extra H2O) still resides in the zeolitic sub-nanocavities; such molecules are spontaneously released after a few days at atmospheric pressure. The actual compressibility of paulingite-K is that obtained by the compression experiment in silicone-oil, with an isothermal bulk modulus K0 = β0-1 = 18.0(1.1) GPa. Paulingite appears to be one of the softest zeolite ever found.",
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High-pressure behavior and crystal-fluid interaction under extreme conditions in paulingite [PAU-topology]. / Gatta, G. Diego; Scheidl, Katharina S.; Pippinger, Thomas; Skála, Roman; Lee, Yongjae; Miletich, Ronald.

In: Microporous and Mesoporous Materials, Vol. 206, No. C, 01.04.2015, p. 34-41.

Research output: Contribution to journalArticle

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